EP0391620A1 - Verfahren zur Erniedrigung der Verschmutzung in Ethylencracköfen - Google Patents

Verfahren zur Erniedrigung der Verschmutzung in Ethylencracköfen Download PDF

Info

Publication number
EP0391620A1
EP0391620A1 EP90303424A EP90303424A EP0391620A1 EP 0391620 A1 EP0391620 A1 EP 0391620A1 EP 90303424 A EP90303424 A EP 90303424A EP 90303424 A EP90303424 A EP 90303424A EP 0391620 A1 EP0391620 A1 EP 0391620A1
Authority
EP
European Patent Office
Prior art keywords
ethylene
triphenylphosphine oxide
fouling
ethylene cracking
furnace
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP90303424A
Other languages
English (en)
French (fr)
Other versions
EP0391620B1 (de
Inventor
John C. Kisalus
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ChampionX LLC
Original Assignee
Nalco Chemical Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nalco Chemical Co filed Critical Nalco Chemical Co
Priority to AT90303424T priority Critical patent/ATE86650T1/de
Publication of EP0391620A1 publication Critical patent/EP0391620A1/de
Application granted granted Critical
Publication of EP0391620B1 publication Critical patent/EP0391620B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
    • C10G9/16—Preventing or removing incrustation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/04—Thermal processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/20—Use of additives, e.g. for stabilisation

Definitions

  • Ethylene manufacture entails the use of pyrolysis or "cracking" furnaces to manufacture ethylene from various gaseous and liquid petroleum feed stocks.
  • Typical gaseous feed stocks include ethane, butane and mixtures thereof.
  • Typical liquid feed stocks include naphthas, kerosene, gas oil and crude oil.
  • Fouling of the cracking furnace coils and transfer line exchangers occurs due to coking and polymer deposition.
  • the fouling problem probably is the major operational difficulty experienced in running an ethylene plant.
  • ethylene furnaces must be periodically shut down for cleaning.
  • "crash shut downs” are sometimes required due to dangerous increases in pressure or temperatures resulting from deposit build-up on furnace coils and TLE's. Cleaning operations are carried out either mechanically or by steam/air decoking.
  • Run lengths for ethylene furnaces average from one week to three months depending in part upon the rate of fouling of the furnace coils and TLE's. This fouling rate is in turn dependent upon the nature of the feed stock as well as upon furnace design and operating parameters. In general, however, heavier feed stocks and higher cracking severity result in an increased rate of furnace and TLE fouling.
  • amine neutralized sulfonate treatments have been used in some ethylene plants to reduce furnace coil fouling. These compounds, however, have failed to prevent coking and fouling of TLE's immediately down stream of the furnace. The failure in respect of the TLE's may be due to premature degradation of the treatments in the ethylene furnace which sees temperatures in the range 1,000° - 1,700°F (about 535 - 930°C).
  • US-A-4,105,540 teaches that phosphate and phosphite mono and diesters in small amounts function as anti-foulant additives in ethylene cracking furnaces which are subjected to elevated temperature from about 500° - 1,700°F (about 260 - 930°C).
  • US-A-4,542,253 discloses that certain amine neutralization products of the compounds disclosed in US-A-4,105,540 provide an improved ethylene cracking furnace anti-foulant.
  • US-A-3,531,394 shows certain phosphorus compounds as being anti-foulants in steam cracking processes.
  • the invention comprises a method for reducing fouling in ethylene cracking furnaces using petroleum feed stock which comprises treating the petroleum feed stock with an anti-fouling amount of triphenylphosphine oxide, preferably at least 10 ppm and more preferably 25-100 ppm of triphenylphosphine oxide.
  • an anti-fouling amount of triphenylphosphine oxide preferably at least 10 ppm and more preferably 25-100 ppm of triphenylphosphine oxide.
  • plant equipment surfaces be pretreated with this compound.
  • test method involved the utilization of a laboratory reactor which duplicated the conditions found in an ethylene cracking furnace.
  • publications "Kinetics of Coke Deposition in the Thermal Cracking of Propane", K.M. Sundaram and G.F. Froment, Chemical Engineering Science , 1979, Vol. 34 pp. 635-644; and "Coke Deposition in the Thermal Cracking of Ethane", K.M. Sundaram, P.S. VanDamme, and G.F. Froment, A1ChE Journal , November 1981, Vol. 27, No. 6, pg. 946.
  • triphenylphosphine oxide containing 2.36% P was prepared to compare its effectiveness with that of triphenylphosphine.
  • Fig. 1 shows the effectiveness of the additive by comparing asymptotic coking rates of blank runs with those obtained from continuous addition experiments of triphenylphosphine oxide.
  • Fig. 3 compares the effect of triphenylphosphine vs. triphenylphosphine oxide on the asymptotic coking rates.
  • Fig. 4 shows correlation between CH4 yield and conversion.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fireproofing Substances (AREA)
EP90303424A 1989-04-03 1990-03-30 Verfahren zur Erniedrigung der Verschmutzung in Ethylencracköfen Expired - Lifetime EP0391620B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT90303424T ATE86650T1 (de) 1989-04-03 1990-03-30 Verfahren zur erniedrigung der verschmutzung in ethylencrackoefen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US332649 1989-04-03
US07/332,649 US4900426A (en) 1989-04-03 1989-04-03 Triphenylphosphine oxide as an ethylene furnace antifoulant

Publications (2)

Publication Number Publication Date
EP0391620A1 true EP0391620A1 (de) 1990-10-10
EP0391620B1 EP0391620B1 (de) 1993-03-10

Family

ID=23299207

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90303424A Expired - Lifetime EP0391620B1 (de) 1989-04-03 1990-03-30 Verfahren zur Erniedrigung der Verschmutzung in Ethylencracköfen

Country Status (7)

Country Link
US (1) US4900426A (de)
EP (1) EP0391620B1 (de)
JP (1) JPH02286628A (de)
AT (1) ATE86650T1 (de)
CA (1) CA2004252A1 (de)
DE (1) DE69001034T2 (de)
ES (1) ES2040047T3 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009108566A3 (en) * 2008-02-25 2009-11-26 Baker Hughes Incorporated Method for reducing fouling in furnaces

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5360531A (en) * 1992-12-10 1994-11-01 Nalco Chemical Company Phosphoric triamide coking inhibitors
US5354450A (en) * 1993-04-07 1994-10-11 Nalco Chemical Company Phosphorothioate coking inhibitors
US5779881A (en) * 1994-02-03 1998-07-14 Nalco/Exxon Energy Chemicals, L.P. Phosphonate/thiophosphonate coking inhibitors
DE4405883C1 (de) * 1994-02-21 1995-08-10 Gerhard Prof Dr Zimmermann Verfahren zur Herstellung von thermisch gecrackten Produkten und Anwendung des Verfahrens zur Verminderung der Verkokung von Wärmeaustauschflächen
DE4405884C1 (de) * 1994-02-21 1995-09-07 Mannesmann Ag Wärmeaustauschfläche in Reaktoren und/oder Wärmeaustauschern und Verfahren zur Herstellung einer katalytisch desaktivierten Metalloberfläche
US5863416A (en) * 1996-10-18 1999-01-26 Nalco/Exxon Energy Chemicals, L.P. Method to vapor-phase deliver heater antifoulants

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3531394A (en) * 1968-04-25 1970-09-29 Exxon Research Engineering Co Antifoulant additive for steam-cracking process
US4105540A (en) * 1977-12-15 1978-08-08 Nalco Chemical Company Phosphorus containing compounds as antifoulants in ethylene cracking furnaces
US4542253A (en) * 1983-08-11 1985-09-17 Nalco Chemical Company Use of phosphate and thiophosphate esters neutralized with water soluble amines as ethylene furnace anti-coking antifoulants
US4835332A (en) * 1988-08-31 1989-05-30 Nalco Chemical Company Use of triphenylphosphine as an ethylene furnace antifoulant

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3647677A (en) * 1969-06-11 1972-03-07 Standard Oil Co Retardation of coke formation
CA935190A (en) * 1970-05-20 1973-10-09 Koszman Ihor Thermal cracking process
US4551227A (en) * 1984-04-16 1985-11-05 Phillips Petroleum Company Antifoulants for thermal cracking processes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3531394A (en) * 1968-04-25 1970-09-29 Exxon Research Engineering Co Antifoulant additive for steam-cracking process
US4105540A (en) * 1977-12-15 1978-08-08 Nalco Chemical Company Phosphorus containing compounds as antifoulants in ethylene cracking furnaces
US4542253A (en) * 1983-08-11 1985-09-17 Nalco Chemical Company Use of phosphate and thiophosphate esters neutralized with water soluble amines as ethylene furnace anti-coking antifoulants
US4835332A (en) * 1988-08-31 1989-05-30 Nalco Chemical Company Use of triphenylphosphine as an ethylene furnace antifoulant

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009108566A3 (en) * 2008-02-25 2009-11-26 Baker Hughes Incorporated Method for reducing fouling in furnaces
US8192613B2 (en) 2008-02-25 2012-06-05 Baker Hughes Incorporated Method for reducing fouling in furnaces

Also Published As

Publication number Publication date
EP0391620B1 (de) 1993-03-10
CA2004252A1 (en) 1990-10-03
DE69001034T2 (de) 1993-07-29
ES2040047T3 (es) 1993-10-01
JPH02286628A (ja) 1990-11-26
ATE86650T1 (de) 1993-03-15
US4900426A (en) 1990-02-13
DE69001034D1 (de) 1993-04-15

Similar Documents

Publication Publication Date Title
EP1054050B1 (de) Verfahren zur Versorgung eines Rohres mit Kohlenmonoxidhemmenden Eigenschaften beim thermischen Kracken von Kohlenwasserstoffen
CA2152335C (en) Method for treating the radiant tubes in a thermal cracking process
US4835332A (en) Use of triphenylphosphine as an ethylene furnace antifoulant
US5354450A (en) Phosphorothioate coking inhibitors
EP0391620B1 (de) Verfahren zur Erniedrigung der Verschmutzung in Ethylencracköfen
US4167471A (en) Passivating metals on cracking catalysts
US5360531A (en) Phosphoric triamide coking inhibitors
EP0168984A1 (de) Verbesserungen beim Betrieb von Raffinieranlagen und von petrochemischen Anlagen
EP0698650A1 (de) Methode zur Erhöhung der Ausbeute an schwerem Kohlenwasserstoffe in einem thermischen Crackverfahren
US4663018A (en) Method for coke retardant during hydrocarbon processing
EP0714969B1 (de) Hemmung von Verschmutzung der Koksanlagerung in Kohlenwasserstoffbehandlungsapparatur
EP0852256B1 (de) Eine Methode zum Koksablagerungsinhibitoren mit Phosphonate/Thiophosphonate
US5039391A (en) Use of boron containing compounds and dihydroxybenzenes to reduce coking in coker furnaces
US5093032A (en) Use of boron containing compounds and dihydroxybenzenes to reduce coking in coker furnaces
KR100453302B1 (ko) 히터 오염 방지제의 증기상 전달 방법
KR100352923B1 (ko) 탄화수소의열분해분해중에생성되는코우크스의분쇄를촉진하는방법
EP0601609B1 (de) Der Einhalt der Koksbindung mit Phosphorsäure-Triamide
CA2263043C (en) Method for reducing carbon monoxide in the cracking of hydrocarbon gas streams
MXPA97008014A (en) Method for the supply, in steam phase, of anti-cranks for heating

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

17P Request for examination filed

Effective date: 19901224

17Q First examination report despatched

Effective date: 19920423

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19930310

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19930310

Ref country code: DK

Effective date: 19930310

Ref country code: CH

Effective date: 19930310

REF Corresponds to:

Ref document number: 86650

Country of ref document: AT

Date of ref document: 19930315

Kind code of ref document: T

REF Corresponds to:

Ref document number: 69001034

Country of ref document: DE

Date of ref document: 19930415

ITF It: translation for a ep patent filed
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2040047

Country of ref document: ES

Kind code of ref document: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
EAL Se: european patent in force in sweden

Ref document number: 90303424.7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 19960315

Year of fee payment: 7

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19970213

Year of fee payment: 8

Ref country code: FR

Payment date: 19970213

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19970217

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19970218

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19970225

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19970226

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19970317

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970331

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 19970403

Year of fee payment: 8

REG Reference to a national code

Ref country code: ES

Ref legal event code: PC2A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980330

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980330

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980330

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980331

Ref country code: FR

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19980331

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980331

BERE Be: lapsed

Owner name: NALCO/EXXON ENERGY CHEMICAL L.P. A DELAWARE LTD P

Effective date: 19980331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981001

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19980330

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19981001

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981201

EUG Se: european patent has lapsed

Ref document number: 90303424.7

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 19990201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050330